JPH0518623B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a cationic surfactant characterized in that it has one of a urea-binding group, a thiourea-binding group, or a carbonamide group in its branched chain, and a cationic group in its main chain. and an anionic surfactant. Conventionally, cationic surfactants have been used in a variety of applications that utilize the properties of cationic groups, such as antistatic agents for fibers, dyeing aids, flotation agents, metal anticorrosives, bactericides, and emulsifiers. These are generally expressed as R-B-ZX, in which a hydrophobic chain (R) and a cationic hydrophilic group (Z) are linked via a divalent linking group (B), and an anionic group (X) is linked as a counterion. It has a structure that allows However, these conventional cationic surfactants precipitate when mixed with anionic surfactants in a solution, as described in Surfactant Handbook (Sangyo Tosho Co., Ltd., 1966 edition), page 9. It is known that the two cannot be used together, and it is widely recognized that poor compatibility with anionic surfactants is a serious drawback of cationic surfactants. Anionic surfactants are well known as cleaning agents,
They are used in an extremely wide variety of applications, such as wetting agents, foaming agents, and emulsifiers.For this reason, when using cationic surfactants, it is necessary to sufficiently remove the influence of anionic surfactants; When using a surfactant, it is necessary to sufficiently remove the cationic surfactant before use. Such a removal operation is not only complicated in terms of process, but also the influence of the surfactant that remains without being sufficiently removed may reduce the effectiveness of the different ionic surfactant used in the subsequent process, or The reality is that there are many cases where this is not possible. In view of these circumstances, the present inventors conducted intensive research on the development of cationic surfactants that have excellent compatibility with anionic surfactants. A cationic surfactant having either one group or a carbonamide group is soluble in hard water containing a large amount of inorganic salts such as seawater, and in water over a wide pH range, and anionic surfactants. We discovered that it has excellent compatibility and does not reduce its surfactant properties even when used in combination with
The present invention has now been completed. That is, the cationic surfactant according to the present invention is represented by the following general formula (). However, in the formula, R is a hydrocarbon group having 4 to 20 carbon atoms, a perfluoroalkyl group, or a perfluoroalkenyl group, and A represents a trivalent linking group. _Q1
is (-CH ₂ ) _l --, (-CH ₂ ) _l --O(-CH ₂ ) _p --(
however,
l and p represent integers from 2 to 6. ),or

[Formula] (wherein R ₆ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), R ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. Y represents an oxygen atom or a sulfur atom. a represents 0 or 1. R ₂ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, or an alkyl group containing one or two ether oxygen atoms. R ₃ , R ₄ and R ₅ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, or an alkyl group containing one ether oxygen, and these may be the same or different. In addition, R ₃ and R ₄ contain a bonded nitrogen atom and are a morpholone group.

It may form a ring like [Formula]. X is an inorganic or organic anion. In the cationic surfactant () according to the present invention, the hydrophobic group R is a hydrocarbon group having 4 to 20 carbon atoms (particularly preferably an alkyl group or an alkenyl group)
Alternatively, it is a perfluoroalkyl group or a perfluoroalkenyl group, and may have a linear, branched, or cyclic structure. A is a trivalent linking group,

【formula】

【formula】

[Formula] (where i represents an integer from 1 to 5),

【formula】

[expression] or

[Formula]. The inorganic or organic anion X is specifically Cl, Br, I, CH ₃ SO ₄ , OH,
These include ClO ₄ , NO ₃ , CH ₃ COO or a phosphoric acid group. Examples of the cationic surfactant of the present invention include the following. The cationic surfactant () according to the present invention is
It can be produced in high yield and at low cost by the following production method. That is, the general formula [In the formula, R, A, Q ₁ , R ₁ , Y, a, and R ₂ are as described above. ] A fluorine-containing compound represented by the general formula [In the formula, R, A, Q ₁ , R ₁ , Y, a, and R ₂ are as described above. ] to obtain a fluorine-containing compound represented by [In the formula, R ₃ and R ₄ are as described above. ] by reacting the amine compound represented by the general formula [In the formula, R, A, Q ₁ , R ₁ , Y, a, R ₂ , R ₃ , R ₄
is as described above. ] to obtain a compound represented by the general formula X′-R ₅ () [wherein R ₅ is as described above,
They are bromine and iodine atoms. The cationic surfactant (2) according to the present invention is produced by reacting the compound represented by In the above production method, the reaction for obtaining compound () from compound () consists of the following two-stage mechanism. (1st row) (2nd stage) () Alkali catalyst――――――→ () The same reaction solvent can be used for the first and second stages, such as acetone, methyl ethyl ketone,
Ketone solvents such as methyl isobutyl ketone, alcohol solvents such as methanol, ethanol, and isopropyl alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, dimethoxyethane, tetrahydrofuran, and the like are preferred.
The catalyst for the first stage reaction is NaOH, K ₂ CO ₃ ,
LiOH, Ca(OH) ₂ , _CH3ONa , NaI, LiCl,
Examples include NaCl, (C ₂ H ₅ ) ₄ NI, etc., and their related compounds. Among these, NaI, LiCl,
(C ₂ H ₅ ) ₄ NI is particularly preferred. The amount of the catalyst added is 0.01 to 2 times the molar equivalent of the compound (),
Particularly preferred is 0.1 to 1 molar equivalent. The reaction temperature is
30-160°C, particularly preferably 50-120°C. The catalyst for the second stage reaction is selected from a wide range of alkali compounds, including CH ₃ ONa, NaOH, KOH,
Examples include tertiary amines such as triethylamine, and the amount added is preferably 0.8 to 1.2 molar equivalents based on the compound (). In addition, reactions between fluorine-containing compounds () and amine compounds (), and reactions between compounds () and compounds ()
The solvent for the reaction with is selected from a wide range of solvents, such as water, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone and methyl isobutyl ketone, aromatic solvents such as benzene and toluene, ethyl acetate, Examples include ester solvents such as butyl acetate, and ether solvents such as diethyl ether, isopropyl ether, and tetrahydrofuran. The temperature of the reaction between the fluorine-containing compound () and the amine compound () is -10 to 100°C, preferably 0 to 80°C. The amount of the amine compound () to be charged is 1 to 10 molar equivalents, and 1.5 to 5 molar equivalents to the compound ().
Molar equivalents are preferred. The temperature of the reaction between compound () and compound () is 0 to 120°C, preferably 40 to 100°C. The amount of compound () to be charged is 1 to 10 per compound ().
The molar equivalent is preferably 1.5 to 5 molar equivalent. The fluorine-containing compound represented by the general formula () is prepared using the general formula

[Formula] [In the formula, R, A, Q ₁ and R ₁ are as described above. ] and an isocyanate or thioisocyanate compound represented by the general formula R ₂ -N=C=Y,
Furthermore, the general formula

[Formula] [In the formula, R ₂ and Y are as described above. ] It is produced in good yield by reacting with the acid anhydride represented by. Although the mechanism by which the cationic surfactant of the present invention has excellent compatibility with anionic surfactants is unknown, it does not contain a urea-binding group, a thiourea-binding group, or a carbonamide group as a branched chain. When comparing the compatibility with ordinary cationic surfactants, there is no doubt that the functional groups in these branched chains make a decisive contribution to improving compatibility. Next, various surfactant properties of the cationic surfactant according to the present invention will be shown. Synthesis example 1 500ml with dry silica gel tube and stirrer
N-(3-methylaminopropyl) perfluorooctyl sulfonamide in a 3-necked round bottom flask.
57 g (0.1 mol) and 250 ml of sufficiently dehydrated tetrahydrofuran were weighed out under a nitrogen atmosphere, and dissolved with stirring at room temperature. Methyl isocyanate 5.99g
(0.105 mol) in tetrahydrofuran solution
20 ml was added dropwise at room temperature with vigorous stirring. After the dropwise addition was completed, the mixture was stirred at room temperature for 3 hours, and tetrahydrofuran was distilled off under reduced pressure to form a pale yellow solid.
Obtained 52g. Usually, the above procedure yields a product of sufficient purity to be used in the next reaction, but if necessary, it can be recrystallized from chloroform/n-hexane. mp=64.5~65.5℃ Elemental analysis CHNF analysis value (%) 26.5 2.1 6.7 51.4 Calculated value (%) 26.8 2.2 6.7 51.5 IR spectrum 1370cm ^-1 (-SO ₂ Nν _as ) 1645cm ^-1 (N-CO- NH-) NMR spectrum (CD ₃ COCD ₃ solvent, TMS standard) 1.80ppm (m, 2H), 2.90ppm (s, 3H) 3.09ppm (d, 3H), 3.21ppm (m, 4H) Synthesis example 2 N-(3-Methylaminopropyl) perfluorohexyl sulfonamide 90 ml of N-(3-methylaminopropyl) perfluorohexyl sulfonamide was added to a 300 ml three-necked round-bottomed flask equipped with a silica gel drying tube and a stirrer.
(0.191 mol) and 134 g of pyridine, and while stirring vigorously at room temperature, add 29.3 g of acetic anhydride.
(0.287 mol) was gradually added dropwise. After the dropwise addition was completed, the mixture was further stirred at room temperature for 3 hours, and pyridine was distilled off under reduced pressure. 150 ml of distilled water to the resulting viscous solid residue
was added to ripen the crystals. White crystals were collected by filtration, further washed with water, and dried under reduced pressure at 70°C. Yield: 100g. mp=77.0~78.5℃ Elemental analysis CHN analysis value (%) 28.0 2.4 5.7 Calculated value (%) 28.1 2.5 5.5 IR spectrum 1370cm ^-1 (-SO ₃ Nν _as ) 1640cm ^-1 (-CON) NMR spectrum 1.83ppm (m, 2H), 2.04ppm (s, 3H) 3.05ppm (s, 3H), 3.27ppm (t, 2H) 3.48ppm (t, 2H) Synthesis example 3 500ml with cooling condenser and stirrer
62.7 g (0.1 mol) of the fluorine-containing compound obtained in Synthesis Example 1, 60 g of methyl ethyl ketone, 0.42 g (0.01 mol) of LiCl, and 18.5 g (0.2 mol) of epichlorohydrin were weighed into a three-neck round bottom flask. ,70℃
The mixture was stirred for 1.5 hours. Next, 19.2 g (0.0995 mol) of a 28% methanol solution of CH ₃ ONa was added dropwise. After cooling the inside of the system to room temperature, 500 ml of ethyl acetate was added, and the organic layer was washed twice with liquid-liquid using 200 ml of distilled water each time. After drying the organic layer over anhydrous Na ₂ SO ₄ , the solvent was distilled off under reduced pressure. 64.2 g of pale yellow paste was obtained as a residue. This paste was determined by infrared absorption spectrum and ¹ H-NMR spectrum. was identified. 60g of the above light yellow paste, 40g of dimethylamine
% aqueous solution 33.8 g (0.3 mol), and methanol 60
g was weighed into a 300 ml round bottom flask and stirred at 10°C for 48 hours. Excess dimethylamine and solvent were distilled off under reduced pressure to obtain 63.4 g of a pale brown paste as a residue. The infrared absorption spectrum and ¹ H-NMR show that the epoxy ring has completely disappeared, and this paste is was identified. 60g of the above light brown paste, 42.6g of methyl iodide
(0.3 mol), and 200 g of isopropyl alcohol
was weighed into a 500 ml three-necked round bottom flask and stirred at 70°C for 4 hours. Excess methyl iodide and isopropyl alcohol were distilled off under reduced pressure to obtain a light brown solid as a residue. This solid was recrystallized from isopropyl alcohol/n-hexane and dried to obtain 58.6 g of a pale yellow solid. Elemental analysis confirmed that it was the desired compound. mp=78.0℃ C H N F I analysis value (%) 27.3 3.3 6.7 37.6 13.9 Calculated value (%) 27.6 3.2 6.4 37.1 14.6 Synthesis example 4 According to the same method as in Synthesis Example 3, 51.2 g (0.1 mol) of the fluorine-containing compound obtained in Synthesis Example 2 and 1.5 g of NaI
(0.01 mol), epibromohydrin 27.4 g (0.2 mol), 28% methanol solution of CH ₃ ONa 19.2 g
(0.0995 mol), and 28 g of 28% ammonia water
(0.46 mol) using (Pale yellow paste) 49g was obtained. The above compound was dissolved in 100 g of methanol and neutralized with hydrogen iodide. The solvent was distilled off under reduced pressure, and the target compound (pale yellow crystals) was obtained by recrystallizing from chloroform. Elemental analysis C H N F I analysis value (%) 25.6 2.6 5.6 34.7 17.6 Calculated value (%) 25.2 2.9 5.9 34.6 17.8 Example 1 Compatibility of cationic surfactant according to the present invention with anionic surfactant The results regarding the test are shown in Table-1. That is, the cationic surfactant according to the present invention
0.5wt% aqueous solution and the following anionic surfactant
0.5 wt% were mixed in equal amounts, and the state of the aqueous solution 10 minutes after mixing was shown in four stages. 4: Clear, 3: Slightly cloudy, 2: Cloudy, 1: Solid precipitated. Anionic surfactant C ₇ F ₁₅ COOK Sodium hadecyl sulfate Sodium nioleate

【table】

[Table] ｜ ｜

_{C3H7OH _}

[Table] +○

〃 7 28 C ₁₄ H ₂₉ N(CH ₃ ) ₃
D 1
−○

Br

Claims (1)

[Claims] 1 In the branched chain, a urea binding group, a thiourea binding group,
A surfactant composition comprising a cationic surfactant and an anionic surfactant, characterized by having either one of carbonamide groups and a cationic group in the main chain.